Dialkyl amino ethyl amides, their salts and their use as anti-ripening agents

ABSTRACT

Compounds of the formula ##STR1## in which R is alkylene, vinylene, methylvinylene, phenylene, cyclohexenylene, 1,2-dichlorovinylene and ethylidene, R 1  and R 2  are alkyl and R 3  is hydrogen or alkyl or their amine salts and their use in retarding the ripening of picked fruits, vegetables and other merchantable materials of plant origin.

This is a continuation of application Ser. No. 839,468, filed Oct. 4, 1977, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to certain novel dialkyl amino ethyl amides, their amine salts and their use in retarding the ripening of picked fruits, vegetables and other merchantable materials of plant origin.

In the transport of freshly picked unripe fruits, vegetables and other merchandise of a plant nature from their place of origin and during the storage of such merchandise prior to its sale to the consumer, the natural ripening or maturation of the fruit, or vegetable (i.e., the further physiological activity of the tissues) must be controlled and minimized. For example, the distances and time involved in transportation of fruit produced renders it necessary to pick the fruit in unripe condition with the hope that the ripening process can be controlled until the fruit is ready for display or delivery at the consumer point of acceptance. A source of economic loss to the fruit and vegetable grower arises from the necessity of having to pick certain fruits and vegetables such as citrus fruits, bananas, peppers, and the like while they are still green. They are picked in this condition so that they may reach the consumer before over-ripening occurs. Since these fruits and vegetables must thus be harvested before the maximum weight gain occurs, there is considerable economic loss to the grower. It should also be noted that fruits and vegetables picked before they are completely ripe lose palatability.

Control of ripening is usually achieved by means of refrigeration which lowers the general level of metabolism of the plant or vegetable. In addition, it is common practice to provide adequate ventilation in the environment in which the material is stored. However, such procedures often do not delay the ripening long enough causing loss of merchantable fruit, especially when unforeseen transportation delays are encountered. An embodiment of this invention provides a process which delays the ripening of fruits and vegetables so that they may be picked and shipped at a later stage of ripening, and also to retard the sprouting of tubers while in storage.

DESCRIPTION OF THE INVENTION

The amine compounds of the present invention correspond to the structural formula: ##STR2## in which R is alkylene having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, vinylene, phenylene, preferably o-phenylene, cyclohexenylene, preferably 1,2-cyclohex-4-enyl ##STR3## 1,2-dihalo vinylene, preferably 1,2-dichlorovinylene, 1-methyl vinylene, and ethylidene; R¹ and R² are independently alkyl having 1 to 4 carbon atoms, preferably the same and more preferably both methyl or both ethyl and R³ is hydrogen or alkyl having 1 to 6 carbon atoms, preferably 1 to 2 carbon atoms.

The amine compounds of this invention can be utilized for their stated utility as the amine salts of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or acetic acid.

The amine salts of these acids are equally useful in retarding the ripening of picked fruits, vegetables and other merchantable materials of plant origin and can be represented by the following structural formula: ##STR4## where R, R¹, R² and R³ are as defined and A is the anion chloride, bromide, acetate, sulfate or phosphate; and m is 1, 2 or 3. Thus, when A is chloride, bromide or acetate, m is 1; when A is sulfate, m is 2 and when A is phosphate m is 3.

The compounds of this invention can be prepared according to the following general reaction ##STR5## in which R, R¹ and R² are as defined and R³ is as defined excluding hydrogen and X is chlorine or bromine.

Generally, this first reaction is carried out by slowly adding about an equimole amount of the acid chloride or bromide reactant to the amine reactant, preferably to a solution of the amine reactant, and an excess of an acid halide acceptor at a temperature between about -80° C. and 25° C., preferably between about -60° C. and about 0° C., preferably with stirring. The temperature of the reaction mixture is then allowed to rise to a higher temperature to complete the reaction. The desired reaction product is recovered and purified by conventional techniques.

The compounds of this invention where R³ is hydrogen can be prepared according to the following general reaction ##STR6## in which R, R¹ and R² are as defined and R³ is hydrogen.

Generally, this second reaction is carried out by slowly adding an equimole amount of the diamine reactant to a solution of the anhydride reactant at a temperature around 0° C., preferably with stirring. The temperature of the reaction mixture is then allowed to rise to around room temperature to complete the reaction. The desired reaction product is recovered and purified by conventional techniques.

If the hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or acetic acid salt is desired, then the amine compound is prepared as described above and is then neutralized with hydrochloric, hydrobromic, sulfuric, phosphoric or acetic acid, respectively.

The following examples teach the synthesis of representative compounds of this invention.

EXAMPLE I ETHYL-N-(2'-DIETHYLAMINOETHYL)SUCCINAMATE ##STR7##

This example teaches the synthesis of a representative compound according to the general reaction scheme.

First, 20 milliliters (0.05 mole) N,N-diethylethylene diamine, 50 milliliters dry methylene chloride, and 5.2 milliliters (0.065 mole) pyridine were combined in a flask. Next, 9.03 grams (0.06 mole) 3-carboethoxy-propionyl chloride was added at -60° C. with stirring. The temperature was allowed to rise to 0° C. The reaction mixture was then washed with a 200 milliliter portion of water and a 100 milliliter portion of saturated sodium carbonate solution. The organic solution was stripped in vacuum to yield 2.0 grams of the desired product. n_(D) ³⁰ 1.4500.

EXAMPLE II N-DIMETHYLAMINOETHYL SUCCINAMIC ACID ##STR8##

This example teaches the synthesis of a representative compound where R³ is hydrogen.

First, 7.0 grams (0.07 mole) of succinic anhydride was dissolved in 75 milliliters of acetonitrile and added to a flask. To this solution was added 7.1 grams (0.08 mole) N,N-Dimethylethylenediamine at 0° C. with cooling. After the addition was completed, the reaction temperature was allowed to rise slowly to room temperature. The resulting white solid was filtered off and washed with 50 milliliters of ether. Vacuum drying yielded 13.1 grams of the desired product. m.p. 146°-148° C.

The following is a table of certain selected compounds that are preparable according to the procedure described hereto. Compound numbers are assigned to each compound and are used throughout the remainder of the specification.

                  TABLE I                                                          ______________________________________                                          ##STR9##                                                                      Compound                               n.sub.D.sup.30 or                       Number  R             R.sup.1                                                                               R.sup.2                                                                             R.sup.3                                                                             m.p. °C.                         ______________________________________                                         1       CH.sub.2 CH.sub.2                                                                            C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     H    85-87                                   2**     CH.sub.2 CH.sub.2                                                                            CH.sub.3                                                                              CH.sub.3                                                                            H    146-148                                 3       CH.sub.2 CH.sub.2 CH.sub.2                                                                   C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     H    semi-solid                              4       CH.sub.2 CH.sub.2 CH.sub.2                                                                   CH.sub.3                                                                              CH.sub.3                                                                            H    107-110                                 5       HCCH          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     H    122-125                                          ##STR10##    C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     H    137-139                                 7                                                                                       ##STR11##    CH.sub.3                                                                              CH.sub.3                                                                            H    143-145                                 8                                                                                       ##STR12##    CH.sub.3                                                                              CH.sub.3                                                                            H    113-115                                 9                                                                                       ##STR13##    C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     H    semi-solid                              10                                                                                      ##STR14##    CH.sub.3                                                                              CH.sub.3                                                                            H    semi-solid                              11                                                                                      ##STR15##    CH.sub.3                                                                              CH.sub.3                                                                            H    semi-solid                              12      CH.sub.2 CH.sub.2                                                                            CH.sub.3                                                                              CH.sub.3                                                                            CH.sub.3                                                                            1.4709                                  13*     CH.sub.2 CH.sub.2                                                                            C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     1.4500                                  14      CH.sub.2      C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     1.4645                                  15      CH.sub.2 CH.sub.2                                                                            CH.sub.3                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                     209-220                                 16      CH.sub.2      CH.sub.3                                                                              CH.sub.3                                                                            C.sub.2 H.sub.5                                                                     semi-solid                              17                                                                                      ##STR16##    C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     1.4517                                  ______________________________________                                          *Prepared in Example I                                                         **Prepared in Example II                                                 

ANTI-RIPENING EVALUATION TEST

The compounds of Table I were found to be useful in retarding the ripening of picked fruits, vegetables and other merchantable material of plant origin according to the following described evaluation test.

First, a candidate compound is formulated for testing by dissolving it in 10 milliliters of acetone and then diluting with 90 milliliters of water to yield stock solutions of 1000 and 5000 parts per million of the chemical. Appropriate dilutions are made from the 1000 and 5000 parts per million stock solutions to prepare lower concentrations of 10, 100 and 500 parts per million. Finally, 0.01% by weight of the wetting agent, Tween 20® (polyoxyethylene sorbitan monolaurate) is added to the treatment solution that is to be used in the test.

Bananas are used in the anti-ripening test and were obtained from Ecuador and Costa Rica and are subjected to the testing procedures approximately 10 to 14 days after harvest. They were completely green and of a uniform diameter of about one and one-half inches.

Next, the treatment solution is transferred into a plastic bag and the fruit is immersed and shaken for 30 seconds. In each test, two replicates are used per treatment and four replicates for controls. After treatment the bananas are placed in a forced-draft hood to evaporate the treatment solution. After drying, the bananas are placed in sealable plastic bags which contain a one inch diameter hole for gaseous exchange. The bags are stored throughout the test period in a controlled environmental chamber at 16° C., 40 to 50% relative humidity and in complete darkness for 12, 14 or 28 days. After the selected period of time, the bananas are inspected for their degree of ripeness. The ripeness rating system that is used is based on the following scale: 1=green, 2=breaker, 3=light green or yellow, 4=table ripe, 5=over-ripe and 6=spoiled.

The degree of activity of certain selected compounds is indicated in Table II.

                  TABLE II                                                         ______________________________________                                         Compound Concentration         Degree of Ripeness*                             Number   (parts per million)                                                                          Days    After Treatment                                 ______________________________________                                         Control                                                                        (1-12)   --            12      5                                                1       5000          12      2                                                2       5000          12      3                                                3       5000          12      3                                                4       5000          12      4                                                5       5000          12      4                                                6       5000          12      3                                                7       5000          12      3                                                8        500          12      3                                                9       5000          12      3                                               10       5000          12      3                                               11       5000          12      5                                               12       5000          12      4                                               Control                                                                        (13-15)  --            28      5                                               13       5000          28      4                                               14       5000          28      1                                               15                                                                             Control                                                                        (16)     --            21      4                                               16        100          21      3                                               Control                                                                        (17)     --            14      4                                               17       5000          14      1                                               ______________________________________                                          *1 = green                                                                     2 = breaker                                                                    3 = light green or yellow                                                      4 = table ripe                                                                 5 = overripe                                                                   6 = spoiled                                                              

As can be determined by a study of the data of Table II, the compounds of this invention cause a lesser degree of ripeness than their control.

The compounds of this invention can be used in concentrated form without adjuvants simply by spraying or dipping the fruit, vegetable or other merchantable material of plant origin. Preferably, the compounds are incorporated in formulations such as emulsions, suspensions, solutions or the like. In the most preferred practice of the invention, the compounds or their salts are utilized as aqueous solutions for treatment of the fruit, vegetable, etc. If necessary, a small amount of a non-aqueous solvent, such as acetone, can be used to add solution of the compound.

In addition, the formulation can contain materials such as waxes, oils, emulsifying agent, dispensing agents, wetting agents, coloring agents, fungicides, etc. These and other conventional additives for fruit or vegetable treating can be used according to procedures well known in the art.

The preferred quantity of the compounds of their salts that is employed to retard the ripening process of fruits, vegetables or other merchantable material of plant origin is from about 0.0001% to 5.0% by weight of fruit, vegetable or other material treated. 

What is claimed:
 1. The compound having the structural formula ##STR17## or a salt thereof wherein the anion is chloride, bromide, acetate, sulfate or phosphate.
 2. A method for retarding the ripening of bananas comprising contacting said bananas with a compound having the structural formula ##STR18## in which R is alkylene having 1 to 4 carbon atoms, vinylene, 1,2-dihalo vinylene, 1-methyl vinylene, and ethylidene; R¹ and R² are independently alkyl having 1 to 4 carbon atoms, and R³ is hydrogen or alkyl having 1 to 6 carbon atoms or a salt thereof wherein the anion is chloride, bromide, acetate, sulfate or phosphate.
 3. A method of claim 2 wherein R is alkylene having 1 to 3 carbon atoms, vinylene, 1,2-dichlorovinylene, 1-methyl vinylene and ethylidene; R¹ and R² are both methyl or both ethyl and R³ is hydrogen or alkyl having 1 to 2 carbon atoms.
 4. A method of claim 2 wherein R is ethylene, R¹ is ethyl, R² is ethyl and R³ is hydrogen.
 5. A method of claim 2 wherein R is 1,2-dichlorovinylene, R¹ is methyl, R² is methyl and R³ is hydrogen.
 6. A method of claim 2 wherein R is 1-methyl vinylene, R¹ is methyl, R² is methyl and R³ is hydrogen.
 7. A method of claim 2 wherein R is ethylene, R¹ is methyl, R² is methyl and R³ is methyl. 